Oxygen scavengers, compositions comprising the scavengers, and articles made from the compositions

ABSTRACT

The disclosure relates to oxygen scavenging molecules, compositions, methods of making the compositions, articles prepared from the compositions, and methods of making the articles. This abstract is intended as a scanning tool for purposes of searching in the particular art and is not intended to be limiting of the present invention.

CROSS REFERENCE TO RELATED APPLICATION

This application is a continuation of U.S. application Ser. No.16/508,282, filed on Jul. 10, 2019, which is a continuation of U.S.application Ser. No. 14/517,643, filed on Oct. 17, 2014, now U.S. Pat.No. 10,351,692, the contents of which are hereby incorporated byreference herein in their entireties.

BACKGROUND

Many polymers used in packaging materials and other articles arepermeable to oxygen. When oxygen permeates a polymeric composition orarticle, it can cause oxidative damage to the contents of the package.It is therefore desirable for certain polymer compositions and articlesto have oxygen scavenging capability, such that when oxygen permeatesthe composition or article, oxidative damage can be mitigated.

It is known in the art to include an oxygen scavenger in the packagingstructure for the protection of oxygen sensitive materials. Suchscavengers are believed to react with oxygen that is trapped in thepackage or that permeates from outside of the package, thus extending tolife of package contents. These packages include films, bottles,containers, and the like. Food, beverages (such as beer and fruitjuices), cosmetics, medicines, and the like are particularly sensitiveto oxygen exposure and require high barrier properties to oxygen topreserve the freshness of the package contents and avoid changes inflavor, texture and color.

Therefore, a need exists for compounds and compositions having improvedoxygen scavenging capacity. These needs and other needs are satisfied bythe present invention.

SUMMARY

In accordance with the purpose(s) of the invention, as embodied andbroadly described herein, the invention, in one aspect, relates tooxygen scavenger molecules and compounds, compositions comprising themolecules and compounds, and articles prepared from the compositions.

Also disclosed are polymer compositions comprising the disclosed oxygenscavenging molecules.

Also disclosed are articles prepared from the disclosed compounds andcompositions.

Also disclosed are methods of making oxygen scavenging molecules andpolymer compositions comprising the disclosed oxygen scavengingmolecules.

Also disclosed are methods for making articles comprising the disclosedcompounds and compositions.

Also disclosed are methods for packaging an oxygen sensitive materialusing the disclosed compounds and compositions.

Also disclosed are the products and articles of the disclosed methods.

Additional advantages of the invention will be set forth in part in thedescription which follows, and in part will be obvious from thedescription, or can be learned by practice of the invention. Theadvantages of the invention will be realized and attained by means ofthe elements and combinations particularly pointed out in the appendedclaims. It is to be understood that both the foregoing generaldescription and the following detailed description are exemplary andexplanatory only and are not restrictive of the invention, as claimed.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a graph depicting oxygen scavenging data for plaquescomprising a representative oxygen scavenger according to the presentinvention.

DETAILED DESCRIPTION

The present invention can be understood more readily by reference to thefollowing detailed description of the invention and the Examplesincluded therein.

Before the present compounds, compositions, articles, systems, devices,and/or methods are disclosed and described, it is to be understood thatthey are not limited to specific synthetic methods unless otherwisespecified, or to particular reagents unless otherwise specified, as suchmay, of course, vary. It is also to be understood that the terminologyused herein is for the purpose of describing particular aspects only andis not intended to be limiting. Although any methods and materialssimilar or equivalent to those described herein can be used in thepractice or testing of the present invention, example methods andmaterials are now described.

Disclosed are the components to be used to prepare the compositions ofthe invention as well as the compositions themselves to be used withinthe methods disclosed herein. These and other materials are disclosedherein, and it is understood that when combinations, subsets,interactions, groups, etc. of these materials are disclosed that whilespecific reference of each various individual and collectivecombinations and permutation of these compounds cannot be explicitlydisclosed, each is specifically contemplated and described herein. Forexample, if a particular compound is disclosed and discussed and anumber of modifications that can be made to a number of moleculesincluding the compounds are discussed, specifically contemplated is eachand every combination and permutation of the compound and themodifications that are possible unless specifically indicated to thecontrary. Thus, if a class of molecules A, B, and C are disclosed aswell as a class of molecules D, E, and F and an example of a combinationmolecule, A-D is disclosed, then even if each is not individuallyrecited each is individually and collectively contemplated meaningcombinations, A-E, A-F, B-D, B-E, B-F, C-D, C-E, and C-F are considereddisclosed. Likewise, any subset or combination of these is alsodisclosed. Thus, for example, the sub-group of A-E, B-F, and C-E wouldbe considered disclosed. This concept applies to all aspects of thisapplication including steps in methods of making and using thecompositions of the invention. Thus, if there are a variety ofadditional steps that can be performed it is understood that each ofthese additional steps can be performed with any specific embodiment orcombination of embodiments of the methods of the invention.

While aspects of the present invention can be described and claimed in aparticular statutory class, such as the system statutory class, this isfor convenience only and one of skill in the art will understand thateach aspect of the present invention can be described and claimed in anystatutory class. Unless otherwise expressly stated, it is in no wayintended that any method or aspect set forth herein be construed asrequiring that its steps be performed in a specific order. Accordingly,where a method claim does not specifically state in the claims ordescriptions that the steps are to be limited to a specific order, it isno way intended that an order be inferred, in any respect. This holdsfor any possible non-express basis for interpretation, including mattersof logic with respect to arrangement of steps or operational flow, plainmeaning derived from grammatical organization or punctuation, or thenumber or type of aspects described in the specification.

Throughout this application, various publications are referenced. Thedisclosures of these publications in their entireties are herebyincorporated by reference into this application in order to more fullydescribe the state of the art to which this pertains. The referencesdisclosed are also individually and specifically incorporated byreference herein for the material contained in them that is discussed inthe sentence in which the reference is relied upon. Nothing herein is tobe construed as an admission that the present invention is not entitledto antedate such publication by virtue of prior invention. Further, thedates of publication provided herein may be different from the actualpublication dates, which can require independent confirmation.

A. Definitions

In this specification and in the claims that follow, reference will bemade to a number of terms, which shall be defined to have the followingmeanings:

All percentages, ratios and proportions herein are by weight, unlessotherwise specified. All temperatures are in degrees Celsius (° C.)unless otherwise specified.

Throughout the description and claims of this specification the word“comprise” and other forms of the word, such as “comprising” and“comprises,” means including but not limited to, and is not intended toexclude, for example, other additives, components, integers, or steps.

As used in the specification and the appended claims, the singular forms“a,” “an” and “the” include plural referents unless the context clearlydictates otherwise. Thus, for example, reference to “a functionalgroup,” “an alkyl,” or “a residue” includes mixtures of two or more suchfunctional groups, alkyls, or residues, and the like.

Ranges can be expressed herein as from “about” one particular value,and/or to “about” another particular value. When such a range isexpressed, another aspect includes from the one particular value and/orto the other particular value. Similarly, when values are expressed asapproximations, by use of the antecedent “about,” it will be understoodthat the particular value forms another aspect. It will be furtherunderstood that the endpoints of each of the ranges are significant bothin relation to the other endpoint, and independently of the otherendpoint. It is also understood that there are a number of valuesdisclosed herein, and that each value is also herein disclosed as“about” that particular value in addition to the value itself. Forexample, if the value “10” is disclosed, then “about 10” is alsodisclosed. It is also understood that each unit between two particularunits are also disclosed. For example, if 10 and 15 are disclosed, then11, 12, 13, and 14 are also disclosed.

As used herein, the terms “optional” or “optionally” means that thesubsequently described event or circumstance may or may not occur, andthat the description includes instances where said event or circumstanceoccurs and instances where it does not.

As used herein, the term “substantially” means that the subsequentlydescribed event or circumstance completely occurs or that thesubsequently described event or circumstance generally, typically, orapproximately occurs. For example, when the specification discloses thatsubstantially all of an agent is released, a person skilled in therelevant art would readily understand that the agent need not becompletely released. Rather, this term conveys to a person skilled inthe relevant art that the agent need only be released to an extent thatan effective amount is no longer unreleased.

As used herein, the term “polymer” refers to a relatively high molecularweight organic compound, natural or synthetic, whose structure can berepresented by a repeated small unit, the monomer (e.g., polyethylene,rubber, cellulose). Synthetic polymers are typically formed by additionor condensation polymerization of monomers.

As used herein, the term “copolymer” refers to a polymer formed from twoor more different repeating units (monomer residues). By way of exampleand without limitation, a copolymer can be an alternating copolymer, arandom copolymer, a block copolymer, or a graft copolymer. It is alsocontemplated that, in certain aspects, various block segments of a blockcopolymer can themselves comprise copolymers.

As used herein, the term “oligomer” refers to a relatively low molecularweight polymer in which the number of repeating units is between two andten, for example, from two to eight, from two to six, or from two tofour. In one aspect, a collection of oligomers can have an averagenumber of repeating units of from about two to about ten, for example,from about two to about eight, from about two to about six, or fromabout two to about four.

As used herein, the term “molecular weight” (MW) refers to the mass ofone molecule of that substance, relative to the unified atomic mass unitu (equal to 1/12 the mass of one atom of carbon-12).

As used herein, the term “number average molecular weight” (M_(n))refers to the common, mean, average of the molecular weights of theindividual polymers. M_(n) can be determined by measuring the molecularweight of n polymer molecules, summing the weights, and dividing by n.M_(n) is calculated by:

${{\overset{\_}{M}}_{n} = \frac{\sum_{i}{N_{i}M_{i}}}{\sum_{i}N_{i}}},$wherein N_(i) is the number of molecules of molecular weight M_(i). Thenumber average molecular weight of a polymer can be determined by gelpermeation chromatography, viscometry (Mark-Houwink equation), lightscattering, analytical ultracentrifugation, vapor pressure osmometry,end-group titration, and colligative properties.

As used herein, the term “weight average molecular weight” (M_(w))refers to an alternative measure of the molecular weight of a polymer.M_(w) is calculated by:

${{\overset{\_}{M}}_{w} = \frac{\sum_{i}{N_{i}M_{i}^{2}}}{\sum_{i}{N_{i}M_{i}}}},$wherein N_(i) is the number of molecules of molecular weight M_(i).Intuitively, if the weight average molecular weight is w, and a randommonomer is selected, then the polymer it belongs to will have a weightof w on average. The weight average molecular weight can be determinedby light scattering, small angle neutron scattering (SANS), X-rayscattering, and sedimentation velocity.

As used herein, the terms “polydispersity” and “polydispersity index”(PDI) refer to the ratio of the weight average to the number average(M_(w)/M_(n)).

As used herein, the term “compatibilizing agent” refers to a smallmolecule or polymer that has both polar and non-polar functional groups.For example, a fatty-acid ester has both polar and non-polar functionalgroups.

A weight percent (wt. %) of a component, unless specifically stated tothe contrary, is based on the total weight of the formulation orcomposition in which the component is included.

As used herein, nomenclature for compounds, including organic compounds,can be given using common names, IUPAC, IUBMB, or CAS recommendationsfor nomenclature. When one or more stereochemical features are present,Cahn-Ingold-Prelog rules for stereochemistry can be employed todesignate stereochemical priority, E/Z specification, and the like. Oneof skill in the art can readily ascertain the structure of a compound ifgiven a name, either by systemic reduction of the compound structureusing naming conventions, or by commercially available software, such asCHEMDRAW™ (Cambridgesoft Corporation, U.S.A.).

A residue of a chemical species, as used in the specification andconcluding claims, refers to the moiety that is the resulting product ofthe chemical species in a particular reaction scheme or subsequentformulation or chemical product, regardless of whether the moiety isactually obtained from the chemical species. Thus, an ethylene glycolresidue in a polyester refers to one or more —OCH₂CH₂O— units in thepolyester, regardless of whether ethylene glycol was used to prepare thepolyester. Similarly, a sebacic acid residue in a polyester refers toone or more —CO(CH₂)₈CO— moieties in the polyester, regardless ofwhether the residue is obtained by reacting sebacic acid or an esterthereof to obtain the polyester.

A very close synonym of the term “residue” is the term “radical,” whichas used in the specification and concluding claims, refers to afragment, group, or substructure of a molecule described herein,regardless of how the molecule is prepared. For example, a2,4-thiazolidinedione radical in a particular compound has the structure

regardless of whether thiazolidinedione is used to prepare the compound.In some embodiments the radical (for example an alkyl) can be furthermodified (i.e., substituted alkyl) by having bonded thereto one or more“substituent radicals.” The number of atoms in a given radical is notcritical to the present invention unless it is indicated to the contraryelsewhere herein.

In some aspects, a structure of a compound can be represented by aformula:

which is understood to be equivalent to a formula:

wherein n is typically an integer. That is, R^(n) is understood torepresent five independent substituents, R^(n(a)), R^(n(b)), R^(n(c)),R^(n(d)), R^(n(e)). By “independent substituents,” it is meant that eachR substituent can be independently defined. For example, if in oneinstance R^(n(a)) is halogen, then R^(n(b)) is not necessarily halogenin that instance.

As used herein, the term “substituted” is contemplated to include allpermissible substituents of organic compounds. In a broad aspect, thepermissible substituents include acyclic and cyclic, branched andunbranched, carbocyclic and heterocyclic, and aromatic and nonaromaticsubstituents of organic compounds. Illustrative substituents include,for example, those described below. The permissible substituents can beone or more and the same or different for appropriate organic compounds.For purposes of this disclosure, the heteroatoms, such as nitrogen, canhave hydrogen substituents and/or any permissible substituents oforganic compounds described herein which satisfy the valences of theheteroatoms. This disclosure is not intended to be limited in any mannerby the permissible substituents of organic compounds. Also, the terms“substitution” or “substituted with” include the implicit proviso thatsuch substitution is in accordance with permitted valence of thesubstituted atom and the substituent, and that the substitution resultsin a stable compound, e.g., a compound that does not spontaneouslyundergo transformation such as by rearrangement, cyclization,elimination, etc.

In defining various terms, “A¹,” “A²,” “A³,” and “A⁴” are used herein asgeneric symbols to represent various specific substituents. Thesesymbols can be any substituent, not limited to those disclosed herein,and when they are defined to be certain substituents in one instance,they can, in another instance, be defined as some other substituents.

The term “alkyl” as used herein is a branched or unbranched saturatedhydrocarbon group of from 1 to 24 carbon atoms, for example from 1 to 12carbons, from 1 to 8 carbons, from 1 to 6 carbons, or from 1 to 4carbons, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,s-butyl, t-butyl, n-pentyl, isopentyl, s-pentyl, neopentyl, hexyl,heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl,tetracosyl, and the like. The alkyl group can be cyclic or acyclic. Thealkyl group can be branched or unbranched. The alkyl group can also besubstituted or unsubstituted. For example, the alkyl group can besubstituted with one or more groups including optionally substitutedalkyl, cycloalkyl, alkoxy, amino, ether, halide, hydroxy, nitro, silyl,sulfo-oxo, or thiol, as described herein. A “lower alkyl” group is analkyl group containing from one to six (e.g., from one to four) carbonatoms.

Throughout the specification “alkyl” is generally used to refer to bothunsubstituted alkyl groups and substituted alkyl groups; however,substituted alkyl groups are also specifically referred to herein byidentifying the specific substituent(s) on the alkyl group. For example,the term “halogenated alkyl” specifically refers to an alkyl group thatis substituted with one or more halide, e.g., fluorine, chlorine,bromine, or iodine. The term “alkoxyalkyl” specifically refers to analkyl group that is substituted with one or more alkoxy groups, asdescribed below. The term “alkylamino” specifically refers to an alkylgroup that is substituted with one or more amino groups, as describedbelow, and the like. When “alkyl” is used in one instance and a specificterm such as “alkylalcohol” is used in another, it is not meant to implythat the term “alkyl” does not also refer to specific terms such as“alkylalcohol” and the like.

This practice is also used for other groups described herein. That is,while a term such as “cycloalkyl” refers to both unsubstituted andsubstituted cycloalkyl moieties, the substituted moieties can, inaddition, be specifically identified herein; for example, a particularsubstituted cycloalkyl can be referred to as, e.g., an“alkylcycloalkyl.” Similarly, a substituted alkoxy can be specificallyreferred to as, e.g., a “halogenated alkoxy,” a particular substitutedalkenyl can be, e.g., an “alkenylalcohol,” and the like. Again, thepractice of using a general term, such as “cycloalkyl,” and a specificterm, such as “alkylcycloalkyl,” is not meant to imply that the generalterm does not also include the specific term.

The term “cycloalkyl” as used herein is a non-aromatic carbon-based ringcomposed of at least three carbon atoms. Examples of cycloalkyl groupsinclude, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, norbornyl, and the like. The term “heterocycloalkyl” is atype of cycloalkyl group as defined above, and is included within themeaning of the term “cycloalkyl,” where at least one of the carbon atomsof the ring is replaced with a heteroatom such as, but not limited to,nitrogen, oxygen, sulfur, or phosphorus. The cycloalkyl group andheterocycloalkyl group can be substituted or unsubstituted. Thecycloalkyl group and heterocycloalkyl group can be substituted with oneor more groups including optionally substituted alkyl, cycloalkyl,alkoxy, amino, ether, halide, hydroxy, nitro, silyl, sulfo-oxo, or thiolas described herein.

The terms “alkoxy” and “alkoxyl” as used herein to refer to an alkyl orcycloalkyl group bonded through an ether linkage; that is, an “alkoxy”group can be defined as —OA¹ where A¹ is alkyl or cycloalkyl as definedabove. “Alkoxy” also includes polymers of alkoxy groups as justdescribed; that is, an alkoxy can be a polyether such as —OA¹-OA² or—OA¹-(OA²)_(a)-OA³, where “a” is an integer of from 1 to 200 and A¹, A²,and A³ are alkyl and/or cycloalkyl groups.

The term “alkenyl” as used herein is a hydrocarbon group of from 2 to 24carbon atoms with a structural formula containing at least onecarbon-carbon double bond. Asymmetric structures such as (A¹A²)C═C(A³A⁴)are intended to include both the E and Z isomers. This can be presumedin structural formulae herein wherein an asymmetric alkene is present,or it can be explicitly indicated by the bond symbol C═C. The alkenylgroup can be substituted with one or more groups including optionallysubstituted alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl,cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester,ether, halide, hydroxy, ketone, azide, nitro, silyl, sulfo-oxo, orthiol, as described herein.

The term “cycloalkenyl” as used herein is a non-aromatic carbon-basedring composed of at least three carbon atoms and containing at least onecarbon-carbon double bound, i.e., C═C. Examples of cycloalkenyl groupsinclude, but are not limited to, cyclopropenyl, cyclobutenyl,cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl,norbornenyl, and the like. The term “heterocycloalkenyl” is a type ofcycloalkenyl group as defined above, and is included within the meaningof the term “cycloalkenyl,” where at least one of the carbon atoms ofthe ring is replaced with a heteroatom such as, but not limited to,nitrogen, oxygen, sulfur, or phosphorus. The cycloalkenyl group andheterocycloalkenyl group can be substituted or unsubstituted. Thecycloalkenyl group and heterocycloalkenyl group can be substituted withone or more groups including optionally substituted alkyl, cycloalkyl,alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl,aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone,azide, nitro, silyl, sulfo-oxo, or thiol as described herein.

The term “alkynyl” as used herein is a hydrocarbon group of 2 to 24carbon atoms with a structural formula containing at least onecarbon-carbon triple bond. The alkynyl group can be unsubstituted orsubstituted with one or more groups including optionally substitutedalkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl,aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether,halide, hydroxy, ketone, azide, nitro, silyl, sulfo-oxo, or thiol, asdescribed herein.

The term “cycloalkynyl” as used herein is a non-aromatic carbon-basedring composed of at least seven carbon atoms and containing at least onecarbon-carbon triple bond. Examples of cycloalkynyl groups include, butare not limited to, cycloheptynyl, cyclooctynyl, cyclononynyl, and thelike. The term “heterocycloalkynyl” is a type of cycloalkenyl group asdefined above, and is included within the meaning of the term“cycloalkynyl,” where at least one of the carbon atoms of the ring isreplaced with a heteroatom such as, but not limited to, nitrogen,oxygen, sulfur, or phosphorus. The cycloalkynyl group andheterocycloalkynyl group can be substituted or unsubstituted. Thecycloalkynyl group and heterocycloalkynyl group can be substituted withone or more groups including optionally substituted alkyl, cycloalkyl,alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl,aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone,azide, nitro, silyl, sulfo-oxo, or thiol as described herein.

The term “aryl” as used herein is a group that contains any carbon-basedaromatic group including benzene, naphthalene, phenyl, biphenyl,phenoxybenzene, and the like. The term “aryl” also includes“heteroaryl,” which is defined as a group that contains an aromaticgroup that has at least one heteroatom incorporated within the ring ofthe aromatic group. Examples of heteroatoms include, but are not limitedto, nitrogen, oxygen, sulfur, and phosphorus. Likewise, the term“non-heteroaryl,” which is also included in the term “aryl,” defines agroup that contains an aromatic group that does not contain aheteroatom. The aryl group can be substituted or unsubstituted. The arylgroup can be substituted with one or more groups including optionallysubstituted alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl,cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester,ether, halide, hydroxy, ketone, azide, nitro, silyl, sulfo-oxo, or thiolas described herein. The term “biaryl” is a specific type of aryl groupand is included in the definition of “aryl.” Biaryl refers to two arylgroups that are bound together via a fused ring structure, as innaphthalene, or are attached via one or more carbon-carbon bonds, as inbiphenyl.

The term “aldehyde” as used herein is represented by the formula —C(O)H.Throughout this specification “C(O)” is a short hand notation for acarbonyl group, i.e., C═O.

The terms “amine” or “amino” as used herein are represented by theformula NA¹A²A³, where A¹, A², and A³ can be, independently, hydrogen oroptionally substituted alkyl, cycloalkyl, alkenyl, cycloalkenyl,alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.

The term “carboxylic acid” as used herein is represented by the formula—C(O)OH.

The term “ester” as used herein is represented by the formula —OC(O)A¹or —C(O)OA¹, where A¹ can be an optionally substituted alkyl,cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, orheteroaryl group as described herein. The term “polyester” as usedherein is represented by the formula -(A¹O(O)C-A²-C(O)O)_(a)— or-(A¹O(O)C-A²-OC(O))_(a)—, where A¹ and A² can be, independently, anoptionally substituted alkyl, cycloalkyl, alkenyl, cycloalkenyl,alkynyl, cycloalkynyl, aryl, or heteroaryl group described herein and“a” is an integer from 1 to 500. “Polyester” is as the term used todescribe a group that is produced by the reaction between a compoundhaving at least two carboxylic acid groups with a compound having atleast two hydroxyl groups.

The term “ether” as used herein is represented by the formula A¹OA²,where A¹ and A² can be, independently, an optionally substituted alkyl,cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, orheteroaryl group described herein. The term “polyether” as used hereinis represented by the formula -(A¹O-A²O)_(a)—, where A¹ and A² can be,independently, an optionally substituted alkyl, cycloalkyl, alkenyl,cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group describedherein and “a” is an integer of from 1 to 500. Examples of polyethergroups include polyethylene oxide, polypropylene oxide, and polybutyleneoxide.

The term “halide” as used herein refers to the halogens fluorine,chlorine, bromine, and iodine.

The term “heterocycle” as used herein refers to single and multi-cyclicaromatic or non-aromatic ring systems in which at least one of the ringmembers is other than carbon. Heterocycle includes pyridinde,pyrimidine, furan, thiophene, pyrrole, isoxazole, isothiazole, pyrazole,oxazole, thiazole, imidazole, oxazole, including, 1,2,3-oxadiazole,1,2,5-oxadiazole and 1,3,4-oxadiazole, thiadiazole, including,1,2,3-thiadiazole, 1,2,5-thiadiazole, and 1,3,4-thiadiazole, triazole,including, 1,2,3-triazole, 1,3,4-triazole, tetrazole, including1,2,3,4-tetrazole and 1,2,4,5-tetrazole, pyridine, pyridazine,pyrimidine, pyrazine, triazine, including 1,2,4-triazine and1,3,5-triazine, tetrazine, including 1,2,4,5-tetrazine, pyrrolidine,piperidine, piperazine, morpholine, azetidine, tetrahydropyran,tetrahydrofuran, dioxane, and the like.

The term “hydroxyl” as used herein is represented by the formula —OH.

The term “ketone” as used herein is represented by the formula A¹C(O)A²,where A¹ and A² can be, independently, an optionally substituted alkyl,cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, orheteroaryl group as described herein.

The term “azide” as used herein is represented by the formula —N₃.

The term “nitro” as used herein is represented by the formula —NO₂.

The term “nitrile” as used herein is represented by the formula —CN.

The term “thiol” as used herein is represented by the formula —SH.

The terms “electron-withdrawing” or “electron-donating” as used hereinrefer to the ability of a substituent to withdraw or donate electronsrelative to that of hydrogen, if hydrogen occupied the same position inthe molecule. These terms are well-understood by one skilled in the artand are discussed, for example, in Advanced Organic Chemistry by J.March, 1985, pp. 16-18. Electron withdrawing groups can include fluoro,chloro, bromo, nitro, acyl, cyano, carboxyl, lower alkenyl, loweralkynyl, carboxaldehyde, carboxyamido, aryl, quaternary ammonium,trifluoro-methyl, alkoxycarbonyl, aryloxycarbonyl, aminocarbonyl,sulfonic, alkanesulfonyl, arylsulfonyl, perfluoroalkanesulfonyl,perfluoroarylsulfonyl, phosphoryl, tertiary amine cation and acombination thereof, among others. Electron donating groups can includesuch groups as hydroxy, lower alkoxy, lower alkyl, amino, loweralkylamino, di(lower alkyl)amino, aryloxy, mercapto, lower alkylthio,lower alkylmercapto and disulfide among others. One skilled in the artwill appreciate that the aforesaid substituents may have electrondonating or electron withdrawing properties under different chemicalconditions.

Certain instances of the above defined terms may occur more than once inthe structural formulae, and upon such occurrence each term shall bedefined independently of the other.

As used herein, the term “effective amount” refers to an amount that issufficient to achieve the desired result or to have an effect on anundesired condition. For example, a “visually effective amount” refersto an amount that is sufficient to achieve the desired result (i.e.,impart color to a composition or an article), but is generallyinsufficient to cause adverse side effects (e.g., warping of a polymericarticle).

As used herein, the term “leaving group” refers to an atom (or a groupof atoms) with electron withdrawing ability that can be displaced as astable species, taking with it the bonding electrons. Examples ofsuitable leaving groups include sulfonate esters, including triflate,mesylate, tosylate, brosylate, and halides.

Compounds described herein can contain one or more double bonds and,thus, potentially give rise to cis/trans (E/Z) isomers, as well as otherconformational isomers. Unless stated to the contrary, the inventionincludes all such possible isomers, as well as mixtures of such isomers.

Unless stated to the contrary, a formula with chemical bonds shown onlyas solid lines and not as wedges or dashed lines contemplates eachpossible isomer, e.g., each enantiomer and diastereomer, and a mixtureof isomers, such as a racemic or scalemic mixture. Compounds describedherein can contain one or more asymmetric centers and, thus, potentiallygive rise to diastereomers and optical isomers. Unless stated to thecontrary, the present invention includes all such possible diastereomersas well as their racemic mixtures, their substantially pure resolvedenantiomers, all possible geometric isomers, and pharmaceuticallyacceptable salts thereof. Mixtures of stereoisomers, as well as isolatedspecific stereoisomers, are also included. During the course of thesynthetic procedures used to prepare such compounds, or in usingracemization or epimerization procedures known to those skilled in theart, the products of such procedures can be a mixture of stereoisomers.

B. Compounds and Compositions

1. Oxygen Scavengers

In various aspects, the present invention relates to oxygen scavengingcompounds. In one aspect, the disclosed oxygen scavenging compoundscomprise at least one aryl group attached to a heteroatom. In a furtheraspect, at least one of the methylene positions of the aryl group has nosubstitutions. In a still further aspect, the disclosed oxygenscavenging compounds is an amine-based compound. The oxygen scavengingability of the disclosed compounds can be enhanced, in various aspects,by the presence of a transition metal. In some aspects, the disclosedoxygen scavenging compounds can be polymeric. In other aspects, theoxygen scavenging compounds can be nonpolymeric.

In one aspect, the disclosed oxygen scavenging compounds can have thegeneral structure shown below:

In a further aspect, each Ar is aryl or heteroaryl; each Ar¹ is aryl orheteroaryl; and each Ar¹ is substituted with 0, 1, 2, or 3 groupsindependently selected from halogen, C1-C4 alkyl, electron withdrawinggroups, and electron donating groups, and valence is satisfied. In astill further aspect, each R¹ represents five groups independentlyselected from hydrogen, halogen, C1-C4 alkyl,

electron withdrawing groups, and electron donating groups.

In a further aspect, each Ar² is independently aryl or heteroaryl; andeach Ar² is independently substituted with 0, 1, 2, or 3 groupsindependently selected from halogen, C1-C4 alkyl, electron withdrawinggroups and electron donating groups, and valence is satisfied; and eachR¹⁰ is independently selected from hydrogen, C1-C4 alkyl, —C(O)R²⁰, and—C(O)Ar³. In a still further aspect, each R²⁰ is C1-C4 alkyl; and eachAr³ is phenyl or naphthyl; and each Ar³ is independently substitutedwith 0, 1, 2, or 3 groups independently selected from halogen, C1-C4alkyl, —CO₂R³⁰; electron withdrawing group and electron donating groups,and valence is satisfied.

In a further aspect, each R³⁰ is selected from hydrogen, C1-C4 alkyl,—(CH₂)_(n)OH, and —CH₂Ar⁴; and n is an integer selected from 1 or 2. Ina still further aspect, each Ar⁴ is aryl substituted with 0, 1, 2, and 3groups selected from halogen, C1-C4 alkyl, and —C(O)NHCH₂Ar⁵. In a yetfurther aspect, each Ar⁵ is aryl substituted with 0, 1, 2, or 3 groupsindependently selected from halogen, C1-C4 alkyl,

electron withdrawing groups, and electron donating groups. In a yetfurther aspect, each R⁴⁰ is independently selected from hydrogen, C1-C4alkyl, electron withdrawing groups, and electron donating groups; andeach Ar⁶ is aryl substituted with 0, 1, 2, and 3 groups independentlyselected from hydrogen, C1-C4 alkyl, electron withdrawing groups, andelectron donating groups;

In a further aspect, each R² is independently selected from hydrogen,C1-C4 alkyl, —C(O)R⁵⁰, and —C(O)Ar⁷; each R⁵⁰ is C1-C4 alkyl; each Ar⁷is aryl substituted with 0, 1, 2, and 3 groups independently selectedfrom hydrogen, C1-C4 alkyl, and electron withdrawing groups, andelectron donating groups, and valence is satisfied.

In a further aspect, Ar is aryl; Ar¹ is aryl; and the compound has thestructure:

In a further aspect, Ar is aryl; Ar¹ is aryl; one of the five groupsrepresenting R¹ is

Ar² is aryl; and the compound has the structure:

In a further aspect, Ar is aryl; Ar¹ is aryl; two of the five groupsrepresenting R¹ is

Ar² is aryl; and the compound has the structure:

In a further aspect, Ar is aryl; Ar¹ is aryl; one of the five groupsrepresenting R¹ is

Ar² is aryl; Ar³ is naphthyl; Ar⁴ is phenyl; Ar⁵ is phenyl; and thecompound has the structure:

In a further aspect, Ar is monocyclic. In a still further aspect, Ar ispara or meta substituted phenyl.

In a further aspect, the compound can have the structure

In one aspect, the compound has the structure

In another aspect, the compound has the structure

In another aspect, the compound has the structure

In a further aspect, the oxygen scavenger compound is polymeric orcopolymeric. In a still further aspect, the compound is a polymercomprising at least one residue having the formula:

In a further aspect, each of the at least one residue is covalentlybonded as a repeating unit in the polymer chain, covalently bonded as aside-chain pendant group, or covalently bonded as an end group of thepolymer. In a still further aspect, n is 2, 3, 4, 5, or 6; each Ar isaryl or heteroaryl; each Ar¹ is aryl or heteroaryl; and each Ar¹ issubstituted with 0, 1, 2, or 3 groups independently selected fromhalogen, C1-C4 alkyl, electron withdrawing groups, and electron donatinggroups, and valence is satisfied. In a yet further aspect, each R¹represents 6-n groups independently selected from hydrogen, halogen,C1-C4 alkyl, electron withdrawing groups, and electron donating groups.

In a further aspect, the at least one residue is a repeating unit in thepolymer chain. In a still further aspect, the residue comprises:

In another aspect, the residue comprises:

In a further aspect, the repeating unit comprises:

In a still further aspect, the repeating unit comprises:

In a yet further aspect, R⁶⁰ is phenyl or —(CH₂)_(o)—; and o is aninteger 0 to 10. In a still further aspect, R⁶⁰ is substituted with 0,1, 2, 3, or 4 groups independently selected from electron withdrawinggroups and electron donating groups, and valence is satisfied. In aneven further aspect, m is an integer 2 or greater. For example, m can befrom 2 to about 10,000, or from 2 to about 1,000, or from 2 to about100.

In some aspects, the compound has the structure:

In other aspects, the compound has the structure:

In a further aspect, m is an integer 1 or greater. For example, m can befrom 1 to about 10,000, or from 1 to about 1,000, or from 1 to about100. In a still further aspect, n is an integer 1 or greater. Forexample, n can be from 1 to about 10,000, or from 1 to about 1,000, orfrom 1 to about 100. In an even further aspect, 9 is an integer 1 orgreater. For example, n can be from 1 to about 1,000, or from 1 to about100.

In a further aspect, the alkyl group of the disclosed oxygen scavengingcompound can be a branched or unbranched saturated hydrocarbon group of1 to 24 carbon atoms, e.g. 1 to 18 carbons atoms, 1 to 14 carbon atoms,1 to 12 carbon atoms, 1 to 10 carbon atoms, 1 to 8, 1 to 6 carbon atoms,or 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl,n-butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, octyl, decyl,tetradecyl, hexadecyl, eicosyl, tetracosyl and the like. The alkyl groupcan be substituted or unsubstituted. The alkyl group can be substitutedwith one or more groups including, but not limited to, alkyl,halogenated alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, aldehyde,amino, carboxylic acid, ester, halide, hydroxamate, hydroxy, ketone,nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, or thiol, asdescribed below. The alkyl group can be halogenated, which includes analkyl group that is substituted with one or more halide, e.g., fluorine,chlorine, bromine, or iodine. The alkyl group can also be a lower alkylgroup, which is an alkyl group containing from one to six (e.g., fromone to four) carbon atoms.

In a further aspect, the aryl group of the disclosed oxygen scavengingcompound can be any carbon-based aromatic group including but notlimited to, benzene, naphthalene, phenyl, biphenyl, etc. The aryl groupcan also be heteroaryl, which is defined as an aromatic group that hasat least one heteroatom incorporated within the ring of the aromaticgroup. Examples of heteroatoms include, but are not limited to,nitrogen, oxygen, sulfur, and phosphorus. The aryl group can besubstituted or unsubstituted. The aryl group can be substituted with oneor more groups including, but not limited to, alkyl, halogenated alkyl,alkoxy, alkenyl, alkynyl, aryl, heteroaryl, aldehyde, amino, carboxylicacid, ester, halide, hydroxamate, hydroxy, ketone, nitro, silyl,sulfo-oxo, sulfonyl, sulfone, sulfoxide, or thiol as described herein. Abiaryl group is a specific type of aryl group and is included in thedefinition of aryl. Biaryl refers to two aryl groups that are boundtogether via a fused ring structure, as in naphthalene, or are attachedvia one or more carbon-carbon bonds, as in biphenyl.

In a further aspect, suitable electron withdrawing groups and electronreleasing or donating groups for use in the present invention aregenerally known in the art. Exemplary electron withdrawing groupsinclude nitro, carboxylic acid, esters, for example loweralkyl esters,and cyano. Exemplary electron releasing or donating groups includebranched and straight chain alkyl groups, for example, methyl, ethyl,propyl, isopropyl, butyl, isobutyl, and tert-butyl. Other exemplaryelectron releasing groups include alkoxy, for example methoxy andethoxy. Other exemplary electron releasing groups include thioalkyl.Still other exemplary electron releasing groups include amines, forexample —NH₂, and NH(loweralkyl), and N(loweralkyl)₂.

The oxygen scavenging compound can, in certain aspects be complexed to atransition metal. For example, the oxygen scavenging compound can becomplexed to the transition metal through one or more aryl groups, forexample through pi-cloud complexation. The oxygen scavenging compoundcan also be polymerized via complexation to the transition metal.

2. Oxygen Scavenging Compositions

In various aspects, also described herein are compositions comprisingthe disclosed oxygen scavengers. In one aspect, the disclosedcompositions are oxygen scavenging compositions. Generally, thedisclosed oxygen scavenging composition comprises a base polymer; anoxygen scavenger compound of Formula (I)-(IV) present in an amount offrom about 0.10 to about 10 weight percent of the composition; andoptionally, a transition metal in a positive oxidation state, the metalpresent in an amount of from about 10 ppm to about 400 ppm.

In a further aspect, the oxygen scavenging compositions comprise fromabout 0.10% to about 10% weight percent of the oxygen scavenger. In oneaspect, the compositions comprise from about 0.5% to about 10% by weightof an oxygen scavenger. In still further aspect, the compositionscomprise from about 1% to about 5% by weight of an oxygen scavenger. Ina yet further aspect, the compositions comprise from about 0.1% to about1% by weight of an oxygen scavenger. In a still further aspect, thecompositions comprise from about 0.1% to about 5% by weight of an oxygenscavenger. In an even further aspect, the compositions comprise fromabout 3% to about 10% by weight of an oxygen scavenger. In a stillfurther aspect, embodiment the compositions comprise from about 5% toabout 10% by weight of an oxygen scavenger. In a yet further aspect, thecompositions comprise from about 2% to about 7% by weight of an oxygenscavenger.

In various aspects, the disclosed compositions comprise a base polymer.In a further aspect, the base polymer can comprise one or morehomopolymers or copolymers as described herein. In one aspect, thecompositions can comprise from about 80% to about 99.98% by weight of abase polymer. In a further aspect, the composition comprises from about80% to about 99% by weight of a base polymer. In a still further aspect,the composition comprises from about 85% to about 99% by weight of abase polymer. In a yet further aspect, the composition comprises fromabout 90% to about 99.98% by weight of a base polymer. In an evenfurther embodiment the composition comprises from about 95% to about 99%by weight of a base polymer. In a still further aspect, the compositioncomprises from about 95% to about 99.98% by weight of a base polymer. Ina yet further aspect, the composition comprises from about 97% to about99% by weight of a base polymer.

In a further aspect, a variety of different polymers can be used as thebase polymer. The disclosed compositions enable oxygen scavenging, andthus the base polymer generally includes those polymers that can besubject to oxidation. For example, polymers that exhibit at least someoxygen permeability are useful with the disclosed compositions, at leastinasmuch as the disclosed compositions can reduce the oxidative damageto the polymer.

In a further aspect, the base polymer can be a polymer commonly used inpackaging materials including polyethylene, such as low densitypolyethylene, very low density polyethylene, ultra-low densitypolyethylene, high density polyethylene, and linear low densitypolyethylene; polyesters such as (PET), (PEN) and their copolymers suchas PET/IP; polyvinyl chloride (PVC); polyvinylidene chloride (PVDC); andethylene copolymers such as ethylene/vinyl acetate copolymer,ethylene/alkyl (meth)acrylate copolymers, ethylene/(meth)acrylic acidcopolymers, and ionomers. Blends of different base polymers also can beused.

In a further aspect, the base polymer can include one or more polymersapproved by the U.S. Food and Drug Administration (FDA). Non-limitingexamples include polyethylene terephthalate, polypropylene, andpolyethylene.

In a further aspect, the base polymer comprises a polyester polymer orcopolymer. Preferred polyesters include polymers of phthalic acids, suchas polyethylene terephthalate (PET), or a copolymer thereof. PET, forexample, can be made from terephthalic acid and ethylene glycol. PET canalso be made using dimethyl terephthalate and ethylene glycol. Preferredcopolymers of phthalic acids include copolymers of a phthalic acid andone or more hydroxylated organic compounds. Examples of suitablehydroxylated organic compounds include 1,4-cyclohexandedimethanol,1,2-propanediol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol,2-methyl-1,3-propanediol (2MPDO), 1,6-hexanediol, 1,2-cyclohexanediol,1,4-cyclohexanediol, 1,2-cyclohexanedimethanol,1,3-cyclohexanedimethanol, and diols containing one or more oxygen atomsin the chain, e.g., diethylene glycol, triethylene glycol, dipropyleneglycol, tripropylene glycol, or mixtures of these, and the like.

In a further aspect, the base polymer includes a polyethyleneterephthalate homopolymer and copolymer modified with one or morepolycarboxylic acid modifiers in a cumulative amount of less than about15 mole %, or about 10 mole % or less, or about 8 mole % or less, or oneor more hydroxyl compound modifiers in an amount of less than about 60mol %, or less than about 50 mole %, or less than about 40 mole %, orless than about 15 mole %, or about 10 mole % or less, or about 8 mole %or less and polyethylene naphthalate homopolymers and copolymersmodified with a cumulative amount of less than about 15 mole %, or about10 mole % or less, or about 8 mole % or less, of one or morepolycarboxylic acid modifiers or modified with less than about 60 mol %,or less than about 50 mole %, or less than about 40 mole %, or less thanabout 15 mole %, or about 10 mole % or less, or about 8 mole % or lessof one or more hydroxyl compound modifiers, and blends thereof. In someaspects, the base polymer comprises at least 90 mole %, 92 mole %, or 94mole % ethylene terephthalate repeat units based on the moles of allrepeat units in the polyester polymers.

Polyesters such as PET can be prepared by polymerization proceduresknown in the art sufficient to effect esterification andpolycondensation. Polyester melt phase manufacturing processes includedirect condensation of a dicarboxylic acid with a diol, optionally inthe presence of one or more esterification catalysts, in theesterification zone, followed by polycondensation in the prepolymer andfinishing zones in the presence of a polycondensation catalyst; or esterexchange usually in the presence of a transesterification catalyst inthe ester exchange zone, followed by prepolymerization andpolymerization in the presence of a polycondensation catalyst.

As briefly discussed above, the disclosed compositions can comprise atransition metal in a positive oxidation state. The transition metalenhances the oxygen scavenging properties of the oxygen scavengercompound. Amounts of transition metal in the composition can be greaterthan zero and can be up to 5000 ppm. Generally, the transition metalwill be present in an amount of from about 10 ppm to about 400 ppm. Inone aspect, about 200 ppm of the transition metal is present. In afurther aspect, about 250 ppm of the transition metal is present. Inwall applications (as opposed to master batch applications where moretransition metal is used), it can be preferred to keep the level ofmetal below 300, more preferably 250 ppm. In a further aspect, thetransition metal is present from 30 to 150 ppm. In a further aspect,about 50 ppm of the transition metal is present. In a further aspect,about 100 ppm of the transition metal is present. In a further aspect,about 150 ppm of the transition metal is present.

In a further aspect, the transition metal can be a transition metal fromthe first, second, or third transition series of the Periodic Table. Themetal can be Rh, Ru, or one of the elements in the series of Sc to Zn(e.g., Sc, Ti, V, Cr, M_(n), Fe, Co, Ni, Cu, and Zn). In one aspect, thetransition metal is cobalt. Cobalt can be used in +2 or +3 oxidationstates. In some aspects, it is preferred to use cobalt in the +2oxidation state. In a further aspect, the transition metal is rhodium.For example, rhodium in the +2 oxidation state can be used. Thetransition metal can also be a positive oxidation form of zinc.

In a further aspect, the transition metal can be present as a salt. Thecation of the salt can be the transition metal in a positive oxidationstate. A variety of anions can stabilize the positively chargedtransition metal. Suitable anions for the salts include, but are notlimited to, chloride, acetate, oleate, stearate, palmitate,2-ethylhexanoate, carboxylates, such as neodecanoates, octanoates,acetates, lactates, naphthalates, malates, stearates, acetylacetonates,linoleates, oleates, palmitates, 2-ethylhexanoates, or ethyleneglycolates; or as their oxides, borates, carbonates, dioxides,hydroxides, nitrates, phosphates, sulfates, or silicates, among others.Representative transition metal salts include cobalt (II)2-ethylhexanoate, cobalt oleate, and cobalt (II) neodecanoate. Thetransition metal salt also can be an ionomer, in which case a polymericcounter ion can be present.

In a further aspect, the composition can comprise a colorant in avisually effective amount. A visually effective amount refers to anamount of colorant that results in the composition or an article madetherefrom appear colored to the naked eye. A composition comprising avisually effective amount of colorant can refer to a composition havingat least 0.01% by weight colorant. In a further aspect, the compositioncan comprise at least 0.25% by weight colorant. In a still furtheraspect, the composition can comprise at least 0.5% by weight colorant.The compositions can also comprise up to or even exceed about 3% byweight colorant.

A visually effective amount can be determined, for example, byperforming a spectrophotometric scan of the composition or article usinga wavelength range from 400 to 700 nm (visible region). Specific colorscan be characterized according to their spectral pattern. Every coloralso has its own characteristic L (lightness gradation), a (red togreen) and b (yellow to blue) numbers, which can be used to characterizethe compositions and articles.

The colorant can be a variety of pigments and dyes, many of which arecommercially available. Examples of colorants include without limitationCOLORMATRIX Dark Amber, product code: 189-10034-6, COLORMATRIX Dead LeafGreen, product codes: 284-2801-3 and 84-2801-1, AMERICHEM amber, productcode: 59108-CD1, Champaigne green, and COLORMATRIX amber, product code:189-10100-1.

In various aspects, the composition can include other components such asfillers, crystallization aids, impact modifiers, surface lubricants,denesting agents, stabilizers, ultraviolet light absorbing agents, metaldeactivators, nucleating agents such as polyethylene and polypropylene,phosphate stabilizers and dyestuffs. Typically, the total quantity ofsuch components will be less than about 10% by weight of thecomposition. In some embodiments, the amount of these optionalcomponents is less than about 5% by weight of the composition.

In a further aspect, the composition can comprise a reheat additive.Reheat additives are commonly used in the manufacture of polyesterpolymer compositions used to make stretch blow molded bottles becausethe preforms made from the composition must be reheated prior toentering the mold for stretch blowing into a bottle. Any conventionalreheat additive can be used, such as various forms of black particles,e.g., carbon black, activated carbon, black iron oxide, glassy carbon,silicon carbide, gray particles such as antimony, and other reheatadditives such as silicas, red iron oxide, and the like.

In a further aspect, the composition can also comprise an impactmodifier. Examples of typical impact modifiers useful in the compositioninclude ethylene/acrylate/glycidyl terpolymers and ethylene/acrylatecopolymers in which the acrylate is a methyl or ethyl acrylate or methylor ethyl methacrylate or the corresponding butyl acrylates, styrenebased block copolymers, and various acrylic core/shell type impactmodifiers. The impact modifiers can be used in conventional amounts fromabout 0.1 to about 25 weight percent of the overall composition and, insome aspects, in amounts from about 0.1 to about 10 weight percent ofthe composition.

In many applications, not only are the packaging contents sensitive tothe ingress of oxygen, but the contents may also be affected by UVlight. Fruit juices and pharmaceuticals are two examples of suchcontents. Accordingly, in some aspects, it is desirable to incorporateinto the composition a UV absorbing compound in an amount effective toprotect the packaged contents.

In a further aspect, the disclosed composition or an article madetherefrom can have an Oxygen Transmission Rate (OTR) of less than about0.1 (units of cc/pkg/day or 1-5 cc-mm/mg-day-atm) under standardconditions. In a further aspect, the OTR can be less than 0.03, lessthan 0.01, less than 0.005, or less than 0.001. The OTR is a measure ofhow well the oxygen scavenger compound functions at scavenging oxygenthat permeates the composition or article.

When OTR is expressed for a given composition or article, the units“cc/package/day” (“cc/pkg/day”) are typically employed. The term packagerefers to a barrier between an atmosphere of relatively lower oxygencontent and an atmosphere of relatively higher oxygen content. Typicalbarriers (e.g., packages) include bottles, thermoformed containers, andfilms (e.g., shrink wrap).

Oxygen Transmission Rate (oxygen permeation) can be measured, forexample, as described in U.S. Pat. No. 5,021,515. A material of area Acan be exposed to a partial pressure p of oxygen on the one side and toan essentially zero partial pressure of oxygen on the other side. Thequantity of oxygen emerging on the latter side is measured and expressedas a volume rate dV/dt, the volume being converted to some standardcondition of temperature and pressure. After a certain time of exposure(usually a period of a few days) dV/dt is generally found to stabilize,and a P_(W) value can be calculated from equation below:dV/dt=P _(W) Ap  (1)

P_(W) refers to the permeance of the wall. (Analogy with magneticpermeance and electrical conductance would suggest that P_(W) should bedescribed as “permeance per unit area”, but we are following thenomenclature in Encyclopedia of Polymer Science and Technology, Vol. 2,Wiley Interscience, 1985, page 178.) The standard conditions forexpressing dV/dt are 0° C. and 1 atm (1 atm=101 325 Nm⁻²). If thethickness of the area of wall is substantially constant over the area Awith value T and the wall is uniform through the thickness (i.e., thewall is not a laminated or coated one) then the permeability of thematerial in the direction normal to the wall is calculated from theequation below.dV/dt=P _(M) Ap/T  (2)

For non-scavenging materials, P_(W) and P_(M) are to a reasonableapproximation independent of t and p, and P_(M) of T although they areoften appreciably dependent on other conditions of the measurement suchas the humidity of the atmosphere on the oxygen-rich side and thetemperature of the measurement.

For oxygen-scavenging walls, P_(W) and P_(M) are functions of t becausethe concentrations and activity of scavenger vary with time(particularly as the scavenger is consumed). This typically does notprevent measurement of P_(W) and P_(M) reasonably accurately as afunction of time, because the changes in dV/dt are relatively gradualonce the normal initial equilibration period of a few days is over.After a few days' exposure to the measurement conditions, however, anon-scavenging material typically achieves a steady state in which dV/dtis equal to the rate of oxygen ingress to the wall, while a scavengingmaterial achieves an (almost) steady state in which dV/dt isconsiderably less than the rate of oxygen ingress to the material. Thisbeing the case, it is likely that P_(W) calculated from (1) is afunction of p as well as of t and that P_(M) in (2) is a function of pand T as well as of t. P_(W) and P_(M) for scavenging materials are,strictly speaking, not true permeances and permeabilities at all (sincepermeation and scavenging are occurring simultaneously) but, rather,apparent ones.

Values of P_(W) and P_(M) (except where stated otherwise) are to beunderstood to refer to conditions in which p=0.21 atm, the relativehumidity on the oxygen-rich side of the wall is 50%, the temperature is23° C. and (in the case of P_(M) values) the thickness of the materialof about 0.45 mm. Conditions close to the first three of these, atleast, are conventional in the packaging industry.

For example, OTR can be measured for bottles, for example, bycontrolling the atmosphere on both sides of a sample of bottles andmeasuring the rate of oxygen permeation over time. Typically, thebottles are mounted on a plate such that there are two ports for gasinlet and outlet. The interior of the bottles is separated from theexterior by an air tight seal. After sealing, the interior of the bottleis flushed with N₂ gas (or N₂+H₂ mixture) to remove any oxygen presentbefore mounting on plate. The bottle is then placed in a controlledenvironmental chamber (maintained at 23° C. and 50% RH) such that theexterior of the bottle is at standard atmosphere with ˜21% oxygen. Theinterior of the bottle is continuously flushed with N₂ (or N₂+H₂) at aknown gas flow rate. The outlet of the flushed gases contains oxygenpermeating through the bottle wall. This flushed gas from the bottleinterior is passed over a sensor that is calibrated to measure oxygencontent of the flushed gas. Such measurements of oxygen content are madecontinuously over time until a steady state is reached. This steadystate value is typically reported as Oxygen Transmission Rate (OTR) forthat bottle in the units of cc/package/day. A preferred OTR for PETbottles is less than 0.1 cc/package/day; more preferred is less than0.01 cc/package/day; most preferred for PET bottles is less than 0.001cc/package/day over the shelf life of the packaged product.

In one aspect, a disclosed composition has an OTR of less than that ofan otherwise identical composition in the absence of the oxygenscavenger compound and the transition metal. In a further aspect, adisclosed composition has an OTR of less than about 75%, less than about50%, less than about 25%, less than about 20%, less than about 10%, lessthan about 5%, or less than about 1% of an otherwise identicalcomposition in the absence of the oxygen scavenger compound and thetransition metal.

In one aspect, the invention provides oxygen scavenging compositionsthat react with oxygen in the presence of transition metals and saltsthereof, comprising, an effective amount of a disclosed oxygen scavengercompound.

In a further aspect, the invention provides oxygen scavengingcompositions that react with oxygen in the presence of transition metalsand salts thereof, comprising, an effective amount of a compound ofFormula (I)-(IV).

In a further aspect, the invention provides an oxygen scavenging systemcomprising: (a) an oxygen scavenging composition, comprising a compoundof Formula (I)-(IV); (b) an effective amount of a transition metalcatalyst; and (c) a functional barrier permeable to oxygen.

In a further aspect, the invention also relates to organic materialnormally susceptible to gradual degradation in the presence of oxygenduring use over an extended period containing an antioxidant effective,or oxygen scavenging effective amount of a disclosed oxygen scavengercompound.

In a further aspect, the invention also relates to organic materialnormally susceptible to gradual degradation in the presence of oxygenduring use over an extended period containing an antioxidant effective,or oxygen scavenging effective amount of a compound of Formula (I)-(IV).

C. Methods

In various aspects, the invention relates to methods for making thedisclosed compounds. In a further aspect, oxygen scavengers of thepresent invention can be synthesized by reacting excessmeta-xylylenediamine (MXDA) with phthalide under conditions effective toproduce the desired product, as depicted below:

In some aspects, the hydroxymethyl substituent can be para- to the amidefunctionality. In a further aspect, p-MXBH can be synthesized byreacting 1,4-benzenedimethanol, potassium tert-butoxide, andmeta-xylenediamine in the presence of a N-heterocyclic carbene basedruthenium-catalyst under conditions effective to provide the desiredcompound. For example, in a still further aspect, about 20 mmol of1,4-benzenedimethanol, about 3 mmol potassium tert-butoxide, and about0.6 mmol of N-heterocyclic carbene based ruthenium-catalyst aredissolved in 500 mL of toluene and heated to reflux while vigorousstirring is maintained. In an even further aspect, about 10 mmol ofmeta-xylene diamine is added dropwise into the solution slowly, and thereflux and stirring are maintained for another 24 h. At the end of thereaction, toluene is distilled off to obtain the crude product, which ispurified, for example, by chromatography over silica gel, to producep-MXBH, represented by the structure below:

In some aspects, the hydroxymethyl substituent can be meta- to the amidefunctionality. In a further aspect, m-MXBH can be synthesized byreacting mono-methyl isophthalate, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, 1-hydroxy-7-azabenzotriazole,4-dimethylaminopyridine, m-xylenediamine, and N,N-diisopropylethylamineunder conditions effective to provide the desired compound. For example,in a still further aspect, to a solution of 2.0 mmol mono-methylisophthalate, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimidehydrochloride (0.77 g, 4.0 mmol), 1-hydroxy-7-azabenzotriazole (0.41 g,3.0 mmol) and 4-dimethylaminopyridine (0.25 g, 2.0 mmol) in anhydrousdichloromethane (DCM, 10 mL) can be added m-xylenediamine (0.18 mL, 1.5mmol) and N,N-diisopropylethylamine (1.05 mL, 6.03 mmol). In a yetfurther aspect, the reaction mixture can then be stirred for asufficient duration, washed with 10% aqueous citric acid, and extractedtwice with DCM. The organic layer can then be washed with saturatedaqueous sodium bicarbonate, brine, dried over Na₂SO₄ and concentrated invacuo. The residue can then be purified, for example, by chromatographyover silica gel, to produce m-MXBH, represented by the structure below:

In various aspects, the disclosed oxygen scavengers can have additionalsubstituents. In a further aspect, Cl—NBHB(N-benzyl-2-(hydroxymethyl)benzamide) can be synthesized by reactingmono-methyl isophthalate, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimidehydrochloride, 1-hydroxy-7-azabenzotriazole, 4-dimethylaminopyridine,m-xylenediamine, and N,N-diisopropylethylamine under conditionseffective to provide the desired compound. For example, in a stillfurther aspect, to a solution of 2.0 mmol mono-methyl isophthalate,1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (0.77 g,4.0 mmol), 1-hydroxy-7-azabenzotriazole (0.41 g, 3.0 mmol) and4-dimethylaminopyridine (0.25 g, 2.0 mmol) in anhydrous dichloromethane(DCM, 10 mL) can be added 3-chlorobenzylamine (0.37 mL, 3.0 mmol) andN,N-diisopropylethylamine (1.05 mL, 6.03 mmol). In a yet further aspect,the reaction mixture can then be stirred for a sufficient duration,washed with 10% aqueous citric acid, and extracted twice with DCM. Theorganic layer can then be washed with saturated aqueous sodiumbicarbonate, brine, dried over Na₂SO₄ and concentrated in vacuo. Theresidue can then be purified, for example, by chromatography over silicagel, to produce Cl—NBHB, represented by the structure below:

In various aspects, the disclosed oxygen scavengers can also have othertethering groups comprising other heteroatoms, for example and withoutlimitations, N or S. In a further aspect,4-(aminomethyl)-N-benzylbenzamide can be synthesized by the followingprocedure. In a still further aspect, 15 g (100 mmol) of4-aminomethylbenzoic acid suspended in 150 ml of water can be mixed with30 g of potassium carbonate, and 28 mL (120 mmol) of di-tert-butylcarbonate can be added dropwise under cooling with ice. The reactionsolution can then be stirred at 40° C. for 3 hours and at roomtemperature overnight. After addition of 50 mL of water and 40 g ofcitric acid, the precipitated crystals can be collected by filtration,washed with 50 mL of water and dried under reduced pressure. Thecrystals can then be suspended in 600 mL of methylene chloride stirredat room temperature with 24 g (150.0 mmol) of carbonylbisimidazole (CDI)for 40 minutes and then with 30.0 mL (0.3 mol) of benzylamine overnight.The reaction solution can then be separated between 600 mL of saturatedaqueous sodium hydrogen carbonate and 900 mL of methylene chloride, andthe organic layer washed with 600 mL of saturated aqueous sodiumchloride, dried over anhydrous sodium sulfate and filtered. The filtratecan then be concentrated under reduced pressure. The resulting residuecan then be dissolved in 150 mL of methylene chloride and 150 mL ofmethanol and concentrated with 90 g of silica gel under reduced pressureand purified by chromatography. The intermediate obtained can then bedissolved in 600 mL of 1,4-dioxane and stirred with 600 mL of 4 Mhydrochloric acid/1,4-dioxane at room temperature for 17 hours andconcentrated under reduced pressure to obtain the desire product,represented by the structure:

Further embodiments of the present invention can be prepared usingmethods and modifications known generally in the art.

In a further aspect, the invention relates to methods for making oxygenscavenging polymers. In a still further aspect, the method comprises thesteps of: a) providing a monomer comprising a moiety represented by theformula:

wherein n is 2, 3, 4, 5, or 6; wherein Ar is aryl or heteroaryl; whereinAr¹ is aryl or heteroaryl; and wherein Ar¹ is substituted with 0, 1, 2,or 3 groups independently selected from halogen, C1-C4 alkyl, electronwithdrawing groups, and electron donating groups, and valence issatisfied; and wherein R¹ represents 6-n groups independently selectedfrom hydrogen, halogen, C1-C4 alkyl, electron withdrawing groups, andelectron donating groups; and b) subjecting the monomer to conditionseffective to provide the oxygen scavenging polymer.

In a yet further aspect, conditions effective to provide comprisepolymerization of polyethylene terephthalate. In a still further aspect,conditions effective to provide comprise providing or introducing themonomer during the polymerization of polyethylene terephthalate. In aneven further aspect, the oxygen scavenging polymer has the structure:

wherein m is an integer 1 or greater; wherein n is an integer 1 orgreater; and wherein p is an integer 1 or greater. For example, m can befrom 1 to about 10,000, or from 1 to about 1,000, or from 1 to about100. In a further aspect, n can be from 1 to about 10,000, or from 1 toabout 1,000, or from 1 to about 100. In a still further aspect, p can befrom 1 to about 1,000, or from 1 to about 100.

In another aspect, an oxygen scavenging polymer of the present inventioncan be synthesized by heating and stirring MXBH and stoichiometricamount of di-acid, either neat or dissolved in a solvent, for examplexylene, to a sufficiently high temperature inside a flask equipped witha Dean-Stark trap. In a further aspect, the water condensate can then beremoved from the Dean-Stark trap, which drives the reaction forward. Thereaction completes when water no longer forms.

In a further aspect, the invention also relates to a method of making anoxygen scavenging polymer comprising the step of: functionalizingpolyethylene terephthalate with a moiety represented by the formula:

wherein n is 2, 3, 4, 5, or 6; wherein Ar is aryl or heteroaryl; whereinAr¹ is aryl or heteroaryl; and wherein Ar¹ is substituted with 0, 1, 2,or 3 groups independently selected from halogen, C1-C4 alkyl, electronwithdrawing groups, and electron donating groups, and valence issatisfied; and wherein R¹ represents 6-n groups independently selectedfrom hydrogen, halogen, C1-C4 alkyl, electron withdrawing groups, andelectron donating groups.

In another aspect, an oxygen scavenging polymer of the present inventioncan be synthesized by mixing PET oligomers/polymers with oligomers ofFormula (III-IV) in a melt-condensation or solid-state condensationreactor under typical condensation reaction conditions under vacuum.

In a further aspect, the invention also relates to methods for makingthe disclosed compositions. Various methods exist for making thedisclosed compositions. In one aspect, the composition can be made bymixing the base polymer with the oxygen scavenger compound andoptionally the transition metal. In some aspects, some or part of thetransition metal may already be present in the base polymer prior tomixing, for example if the transition metal is used as a catalyst formaking the base polymer. In some aspects, the base polymer, theoxidizable organic component or oxygen scavenger and the transitionmetal are mixed by tumbling in a hopper. Other optional ingredients canbe added during this mixing process or added to the mixture after theaforementioned mixing or to an individual component prior to theaforementioned mixing step.

When melt processing is desired for the composition, the composition canalso be made by adding each ingredient separately and mixing theingredients just prior to melt processing the composition to form anarticle. In some embodiments, the mixing can be just prior to the meltprocess zone. In other embodiments, one or more ingredients can bepremixed in a separate step prior to bringing all of the ingredientstogether.

In some aspects, the transition metal can be added neat or in a carrier(such as a liquid or wax) to an extruder or other device for making thearticle, or the metal can be present in a concentrate or carrier withthe oxygen scavenger compound, in a concentrate or carrier with the basepolymer, or in a concentrate or carrier with a base polymer/oxygenscavenger compound blend. It is desirable that the addition of thetransition metal does not substantially increase the intrinsic viscosityof the melt in the melt processing zone. Thus, transition metal ormetals can be added in two or more stages, such as once during the meltphase for the production of the base polymer and again once more to themelting zone for making the article.

The melt blend of base polymer, oxygen scavenger compound, andtransition metal catalyst can also be prepared by adding the componentsat the throat of an injection molding machine that: (i) produces apreform that can be stretch blow molded into the shape of the container,(ii) produces a film that can be oriented into a packaging film, (iii)produces a sheet that can be thermoformed into a food tray, or (iv)produces an injection molded container. The mixing section of theextruder should be of a design to produce a homogeneous blend. Suchprocess steps work well for forming carbonated soft drink, water or beerbottles, packaging films and thermoformed trays. The present inventioncan be employed in any of the conventional known processes for producinga polymeric container, film, tray, or other article that would benefitfrom oxygen scavenging.

According to further aspects of the disclosure, the invention providesmethods for packaging an oxygen sensitive material, comprising: (a)preparing a package having a wall comprising at least one layer, atleast one of the layers comprising a composition, the composition,comprising: (i) a base polymer; (ii) at least one compound of Formula(I)-(IV); and (iii) at least one transition metal in a positiveoxidation state, the metal being present in the composition in an amountof 10 to 400 ppm; wherein the compound is present in an amount of about0.10 to 10 weight percent of the composition; (b) introducing the oxygensensitive material into the package; and (c) closing the package.

D. Articles

In further aspects, the present invention also relates to articlescomprising the disclosed compounds and compositions. Various articlescan be prepared from the disclosed compositions. Thus, the articlesprepared from the compositions will also have the composition present inthe article. Suitable articles include vessels and films, such asflexible sheet films, flexible bags, pouches, semi-rigid and rigidcontainers such as bottles (e.g. PET bottles) or metal cans, orcombinations thereof. Typical flexible films and bags include those usedto package various food items and can be made up of one or amultiplicity of layers to form the overall film or bag-like packagingmaterial. The composition of the present invention can be used in one,some or all of the layers of such packaging material.

Specific articles include preforms, containers and films for packagingof food, beverages, cosmetics, pharmaceuticals, and personal careproducts where a high oxygen barrier is needed. Examples of beveragecontainers are bottles for holding water and carbonated soft drinks, andthe invention is particularly useful in bottle applications containingjuices, sport drinks, beer or any other beverage where oxygendetrimentally affects the flavor, fragrance, performance (e.g., vitamindegradation), or color of the drink. The compositions are alsoparticularly useful as a sheet for thermoforming into rigid packages andfilms for flexible structures. Rigid packages include food trays andlids. Examples of food tray applications include dual oven able foodtrays, or cold storage food trays, both in the base container and in thelidding (whether a thermoformed lid or a film), where the freshness ofthe food contents can decay with the ingress of oxygen. The compositionscan also be used in the manufacture of cosmetic containers andcontainers for pharmaceuticals or medical devices.

Other suitable articles include rigid or semi-rigid articles includingplastic, such as those utilized for juices, soft drinks, as well asthermoformed trays or cup normally having thickness in the range of from100 to 1000 micrometers. The walls of such articles can comprise singleor multiple layers of materials. The article can also take the form of abottle or can, or a crown, cap, crown or cap liner, plastisol or gasket.The composition of the present invention can be used as an integrallayer or portion of, or as an external or internal coating or liner of,the formed semi-rigid or rigid packaging article. As a liner, thecomposition can be extruded as a film along with the rigid articleitself, e.g., by coextrusion, extrusion coating, or an extrusionlamination process, so as to form the liner in situ during articleproduction; or alternatively can be adhered by heat and/or pressure, byadhesive, or by any other suitable method.

In a further aspect, the disclosed compositions can be used for forminga layer of a wall which primarily provides oxygen-scavenging (anotherlayer including polymer providing gas barrier without significantscavenging), or as a head-space scavenger (completely enclosed, togetherwith the package contents, by a package wall). When the compositions areused in a wall or as a layer of a wall, the permeability of thecomposition for oxygen is advantageously not more than about 3.0, orabout 1.7, or about 0.7, or about 0.2, or about 0.03cm³-mm/(m²-atm-day). In some aspects, the permeability of thecomposition is not more than about three-quarters of that in the absenceof the oxygen scavenger compound. In other aspects, the permeability isnot more than about one half, one-tenth in certain embodiments, onetwenty-fifth in other embodiments, and not more than one-hundredth ofthat in the absence of the oxygen scavenger compound.

Although it can be preferable from the standpoint of packagingconvenience and/or scavenging effectiveness to employ the presentinvention as an integral or discrete part of the packaging wall, theinvention can also be used as a non-integral component of a packagingarticle such as, for example, a bottle cap liner, adhesive ornon-adhesive sheet insert, sealant, sachet, fibrous mat insert or thelike.

Besides articles applicable for packaging food and beverage, articlesfor packaging other oxygen-sensitive products can also benefit from thepresent invention. Such products would include pharmaceuticals, oxygensensitive medical products, corrodible metals or products, electronicdevices and the like.

In a further aspect, the composition can be used as a master batch forblending with a polymer or a polymer containing component. In suchcompositions, the concentration of the oxygen scavenger compound and thetransition metal will be high enough to allow for the final blendedproduct to have suitable amounts of these components. The master batchcan also contain an amount of the base polymer with which the masterbatch is blended.

Oxygen permeability of an article can be maintained for a longer periodof time by storing the article in a sealed container or under an inertatmosphere such as nitrogen prior to use with oxygen sensitivematerials.

In one aspect, the invention provides containers comprising a filmforming polymer, having at least one wall comprising an effective amountof an oxygen scavenging composition comprising a disclosed oxygenscavenger compound.

In a further aspect, the invention provides containers comprising a filmforming polymer, having at least one wall comprising an effective amountof an oxygen scavenging composition comprising a compound Formula(I)-(IV).

In a further aspect, the invention provides package walls comprising atleast one layer, the layer comprising a composition, the compositioncomprising: (a) a base polymer; (b) at least one compound of Formula(I)-(IV); and (c) at least one transition metal in a positive oxidationstate, the metal being present in the composition in an amount of 10 to400 ppm; wherein the compound is present in an amount of about 0.10 to10 weight percent of the composition.

In a further aspect, the invention provides package walls, comprising acomposition, the composition comprising: (a) one or more outer layers;and (b) one or more inner layers; wherein at least one of the inner orat least one of the outer layers comprises a composition comprising: (1)a base polymer; (2) at least one compound of formula (I)-(IV); and (3)at least one transition metal in a positive oxidation state, the metalbeing present in the composition in an amount of 10 to 400 ppm; whereinthe compound is present in an amount of about 0.10 to 10 weight percentof the composition. In some aspects, the first layer is disposedradially outward from the second layer.

The articles can be made by various methods known in the art. Generally,the articles are prepared by melt processing methods (i.e., a melt ofthe composition). Such processes generally include injection molding,stretch blow molding, extrusion, thermoforming, extrusion blow molding,and (specifically for multilayer structures) coextrusion and laminationusing adhesive tie layers. Orientation, e.g., by stretch blow molding,of the polymer can be used with phthalate polyesters because of theknown mechanical advantages that result.

The melt processing zone for making the article can be operated undercustomary conditions effective for making the intended articles, such aspreforms, bottles, trays, and other articles mentioned above. In oneaspect, such conditions are effective to process the melt withoutsubstantially increasing the intrinsic viscosity of the melt and whichare ineffective at promoting transesterification reactions. In somepreferred aspects, suitable operating conditions effective to establisha physical blend of the base polymer, oxidizable organic component, andtransition metal are temperatures in the melt processing zone within arange of about 250° C. to about 300° C. at a total cycle time of lessthan about 6 minutes, and typically without the application of vacuumand under a positive pressure ranging from about 0 psig (pound-force persquare inch gauge) to about 900 psig. In some embodiments, the residencetime of the melt on the screw can range from about 1 to about 4 minutes.

In one aspect, the invention provides methods for producing a packagingmaterial having a wall with oxygen barrier properties comprising: (a)combining a base polymer with at least one compound of formula (I)-(IV)to form a composition, the composition having at least one transitionmetal in a positive oxidation state, the metal being present in thecomposition in an amount of 10 to 400 ppm; and wherein the compound ispresent in an amount of about 0.10 to 10 weight present of thecomposition; (b) forming the product of step (a) into a wall; and (c)forming a container which comprises the wall.

In a further aspect, the invention provides methods for making anarticle, comprising: (a) forming a melt by combining in a meltprocessing zone: (i) a base polymer; (ii) at least one compound offormula (I)-(IV), and (iii) at least one transition metal in a positiveoxidation state, the metal being present in the composition in an amountof 10 to 400 ppm; wherein the compound is present in an amount of about0.10 to 10 weight present of the composition; (b) forming an articlefrom the melt.

E. Experimental

The following examples are put forth so as to provide those of ordinaryskill in the art with a complete disclosure and description of how thecompounds, compositions, articles, devices and/or methods claimed hereinare made and evaluated, and are intended to be purely exemplary and arenot intended to limit the disclosure. Efforts have been made to ensureaccuracy with respect to numbers (e.g., amounts, temperature, etc.), butsome errors and deviations should be accounted for. Unless indicatedotherwise, parts are parts by weight, temperature is in ° C. or is atambient temperature, and pressure is at or near atmospheric.

1. Example 1: Synthesis ofm-Xylylenediamine-bis(2-(hydroxymethyl)benzamide)

In an exemplary synthetic example, excess amount of neat m-xylenediamine (MXDA) is stirred with phthalide at room temperature forovernight. The white precipitation is filtered and washed with water toyield m-xylylenediamine-bis(2-(hydroxymethyl)benzamide) (MXBH). Thismethod requires large excess amount of MXDA (>10 fold excess) to drivethe reaction to completion, although the excess MXDA can be reused insubsequent batches.

2. Example 2: Synthesis ofm-Xylylenediamine-bis(2-(hydroxymethyl)benzamide)

In another exemplary synthetic example, 1.0 mL of MXDA and 1.9 gphthalide are dissolved in a mixture of 15 mL of EtOH and 0.5 mL of 10%aqueous NaOH solution, stirred at 50° C. for 3 h followed by stirring atroom temperature for another 60 h. The dense white precipitation wasfiltered off and washed with water to yield MXBH of high purity.

3. Example 3: Synthesis of benzoic esters ofm-Xylylenediamine-bis(2-(hydroxymethyl)benzamide)

In another exemplary synthetic example, 404 mg of MXBH, 244 mg ofbenzoic acid and a catalytic amount of antimony (III) oxide was addedinto 1 L of xylene in a flask equipped with a Dean Stark trap and acondenser. The suspension was heated to reflux and maintained, duringwhich time water is collected in the Dean Stark trap. At the end of thereaction when no more water forms, xylene was distilled off underreduced pressure. The solid residue was dissolved in ethyl acetate,filtered and recrystallized in ethyl acetate-hexane to obtain pureproduct.

4. Example 4: Synthesis of polyethylene terephthalate with MXBH-esterSegments (Prophetic)

In another exemplary synthetic example, PET polymers with MXBH-estersegments can be prepared via normal PET synthesis processes fromethylene glycol and terephthalic acid over an appropriate catalyst(antimony (III) oxide, for example), using MXBH as an additive. MXBH canbe introduced as an additive to either a melt-condensation reactionvessel or a solid state polycondensation reactor, or other reactiveextrusion process. The product is expected to possess MXBH-ester oxygenscavenging segments embedded within PET chains. In one aspect, the endgroup of PET polymer, for example, —COOH, can react with the —OH endgroup of MXBH-ester segment to give off water, thereby extending the PETchain with MXBH-ester chain. In another aspect, an “ester exchange”reaction can take place, wherein the ester bond in PET breaks to createnew end groups which can then react with MXBH-end groups. In a furtheraspect, it is believed the chain created from the ester exchangereaction will be shorter. In a still further aspect, the concentrationof such segments can also depend upon the let-down ratio of the MXBHadditive in the condensation reactions.

5. Example 5: Oxygen Scavenging Performance of MXBH in PolyethyleneTerephthalate

Oxygen scavenging performance of the oxygen scavenging compositions ofthe present invention in different resins were evaluated usingOxysense™. Oxygen Transmission Rate can be calculated from OxySensedata. OxySense measurements were carried out in a sealed OxyVial with aRuthenium dye-based sensitizer attached to the inside wall of the vial.Upon illumination at a specific wavelength, the sensitizer gives offluminescence the intensity of which is correlated with the concentrationof the oxygen in the vial. As a result, a trace of oxygen concentrationchange as a function of time can be plotted. The tests can be performedat higher temperatures to speed up the tests.

Polymer compositions comprising the oxygen scavenger compound preparedin Example 1 [m-xylylenediamine-bis(2-(hydroxymethyl)benzamide) or MXBH]were prepared to evaluate oxygen scavenging performance. To a batch of700 g of pre-dried PET resins (at 170° C. for 4 hours in a Piovandryer), MXBH powder was dosed at either 1.4% (wt.) or 2.0% (wt.)let-down ratios, along with CoNDA Catalyst MasterBatch 250 at either1.5% (wt.) or 2.5% (wt). Each polymer composition was mixed well and fedinto a BOY 22 S injection molding machine to mold plaques. The BOY 22 Sinjection molder barrel temperatures during injection molding was 260°C. for both heating zones, and the injection pressure was ˜700 psi. Themold was water cooled prior to testing. The inventive formulations wereprepared according to the parameters provided in Table 1.

TABLE 1 Test No. Resin type MXBH LDR Catalyst (CoNDA) LDR 1 ParaStar7000 1.4% 1.5% 2 ParaStar 7000 1.4% 2.5% 3 ParaStar 7000 2.0% 1.5% 4ParaStar 9000 1.4% 1.5% 5 ParaStar 9000 1.4% 1.5% Parastar 7000 is a PETresin available from Eastman Chemical Co., Kingsport, TN, USA.

As shown in FIG. 1 , all of the representative formulations comprisingMXBH exhibit oxygen scavenging activity.

It will be apparent to those skilled in the art that variousmodifications and variations can be made in the present inventionwithout departing from the scope or spirit of the invention. Otherembodiments of the invention will be apparent to those skilled in theart from consideration of the specification and practice of theinvention disclosed herein. It is intended that the specification andexamples be considered as exemplary only, with a true scope and spiritof the invention being indicated by the following claims.

What is claimed is:
 1. An article of manufacture comprising acomposition comprising: (i) a base polymer; (ii) a compound having astructure represented by a formula:

wherein Ar is aryl or heteroaryl; wherein R¹ represents five groupsindependently selected from hydrogen, halogen, C1-C4 alkyl, electronwithdrawing groups, electron donating groups, and a structurerepresented by a formula:

wherein Ar² is independently aryl or heteroaryl, and wherein Ar² isindependently substituted with 0, 1, 2, or 3 groups independentlyselected from halogen, C1-C4 alkyl, electron withdrawing groups, andelectron donating groups, and wherein valence is satisfied; wherein R¹⁰is independently selected from hydrogen, C1-C4 alkyl, —C(O)R²⁰, and—C(O)Ar³; wherein R²⁰ is C1-C4 alkyl; wherein each Ar³ is phenyl ornaphthyl, and wherein each Ar³ is independently substituted with 0, 1,2, or 3 groups independently selected from halogen, C1-C4 alkyl,—CO₂R³⁰, electron withdrawing groups, and electron donating groups, andwherein valence is satisfied; wherein R³⁰, when present, is selectedfrom hydrogen, C1-C4 alkyl, —(CH₂)_(n)OH, and —CH₂Ar⁴; wherein n is aninteger selected from 1 or 2; wherein Ar⁴, when present, is arylsubstituted with 0, 1, 2, and 3 groups selected from halogen, C1-C4alkyl, and —C(O)NHCH₂Ar⁵;  wherein each Ar⁵, when present, is arylsubstituted with 0, 1, 2, or 3 groups independently selected fromhalogen, C1-C4 alkyl, electron withdrawing groups, electron donatinggroups, and a structure represented by a formula:

 wherein each R⁴⁰, when present, is independently selected fromhydrogen, C1-C4 alkyl, electron withdrawing groups, and electrondonating groups;  wherein each Ar⁶, when present, is aryl substitutedwith 0, 1, 2, and 3 groups independently selected from hydrogen, C1-C4alkyl, electron withdrawing groups, and electron donating groups;wherein R² is independently selected from hydrogen, C1-C4 alkyl,—C(O)R⁵⁰, and —C(O)Ar⁷; wherein R⁵⁰ is C1-C4 alkyl; wherein each Ar⁷ isaryl substituted with 0, 1, 2, and 3 groups independently selected fromhydrogen, C1-C4 alkyl, and electron withdrawing groups, and electrondonating groups, and valence is satisfied; and (iii) at least onetransition metal in a positive oxidation state.
 2. A method of making anoxygen scavenging polymer comprising the steps of: (a) providing amonomer comprising a moiety represented by a formula:

wherein n is 2, 3, 4, 5, or 6; wherein Ar is aryl or heteroaryl; whereinR¹ represents 6-n groups independently selected from hydrogen, halogen,C1-C4 alkyl, electron withdrawing groups, and electron donating groups;and (b) polymerizing polyethylene terephthalate in the presence of themonomer, or functionalizing polyethylene terephthalate with the monomer.3. The method of claim 2, wherein the method comprises polymerizingpolyethylene terephthalate in the presence of the monomer.
 4. The methodof claim 2, wherein the method comprises functionalizing polyethyleneterephthalate with the monomer.
 5. A wall of a package comprising atleast one layer, said layer comprising a composition comprising: (i) abase polymer; (ii) a compound having a structure represented by aformula:

wherein Ar is aryl or heteroaryl; wherein R¹ represents five groupsindependently selected from hydrogen, halogen, C1-C4 alkyl, electronwithdrawing groups, electron donating groups, and a structurerepresented by a formula:

wherein Ar² is independently aryl or heteroaryl, and wherein Ar² isindependently substituted with 0, 1, 2, or 3 groups independentlyselected from halogen, C1-C4 alkyl, electron withdrawing groups, andelectron donating groups, and wherein valence is satisfied; wherein R¹⁰is independently selected from hydrogen, C1-C4 alkyl, —C(O)R²⁰, and—C(O)Ar³; wherein R²⁰ is C1-C4 alkyl; wherein each Ar³ is phenyl ornaphthyl, and wherein each Ar³ is independently substituted with 0, 1,2, or 3 groups independently selected from halogen, C1-C4 alkyl,—CO₂R³⁰, electron withdrawing groups, and electron donating groups, andwherein valence is satisfied; wherein R³⁰, when present, is selectedfrom hydrogen, C1-C4 alkyl, —(CH₂)_(n)OH, and —CH₂Ar⁴; wherein n is aninteger selected from 1 or 2; wherein Ar⁴, when present, is arylsubstituted with 0, 1, 2, and 3 groups selected from halogen, C1-C4alkyl, and —C(O)NHCH₂Ar⁵;  wherein each Ar⁵, when present, is arylsubstituted with 0, 1, 2, or 3 groups independently selected fromhalogen, C1-C4 alkyl, electron withdrawing groups, electron donatinggroups, and a structure represented by a formula:

 wherein each R⁴⁰, when present, is independently selected fromhydrogen, C1-C4 alkyl, electron withdrawing groups, and electrondonating groups;  wherein each Ar⁶, when present, is aryl substitutedwith 0, 1, 2, and 3 groups independently selected from hydrogen, C1-C4alkyl, electron withdrawing groups, and electron donating groups;wherein R² is independently selected from hydrogen, C1-C4 alkyl,—C(O)R⁵⁰, and —C(O)Ar⁷; wherein R⁵⁰ is C1-C4 alkyl; wherein each Ar⁷ isaryl substituted with 0, 1, 2, and 3 groups independently selected fromhydrogen, C1-C4 alkyl, and electron withdrawing groups, and electrondonating groups, and valence is satisfied; and (iii) at least onetransition metal in a positive oxidation state.
 6. The wall of claim 5,wherein said wall comprises (a) one or more outer layers; and (b) one ormore inner layers; wherein at least one of said inner or at least one ofsaid outer layers comprises the composition.